Fragrance releasing non-volatile polymeric-siloxanes

ABSTRACT

A fragrance releasing siloxane comprising a substituent having the formula (R 1  O) a  (R 2  O) b  (R 3  O) c  (R 4 ) d  (R 5 ) e  SiR U  with R U  a two to forty atom divalent hydrocarbon radical where R 1  O, R 2  Oand R 3  O are each independently fragrant alkoxide moieties, derived from the alcohols R 1  OH, R 2  OH and R 3  OH wherein R 1  OH, R 2  OH and R 3  OH are independently fragrant alcohols with R 4  and R 5  selected from the group consisting of monovalent hydrocarbon radicals having from one to forty carbon atoms and monovalent alkoxy radicals having from one to forty carbon atoms, where the subscript a has a value ranging from 1 to 3 and the subscripts b, c, d, and e have values ranging from 0 to 2 subject to the limitation that a+b+c+d+e=3.

FIELD OF THE INVENTION

The present invention relates to non-volatile oligomeric or polymericsiloxanes which may be linear, branched or cross-linked, suitable foruse in a variety of applications including personal care formulations,house-hold products, automotive, textiles and molding materials whereinthe non-volatile polymeric siloxane has been chemically modified torelease a fragrant molecule upon hydrolysis. The present inventionfurther relates to such molecules where the rate of fragrant moleculerelease is sufficiently slow so that products formulated with themodified polymeric non-volatile siloxane exhibit a desirable fragrancefor long periods of time.

BACKGROUND OF THE INVENTION

The slow sustained release of a fragrant molecule is a highly desirabletrait in many personal care products. A number of means have beenproposed and implemented to achieve this goal. Among these means aredissolving or suspending fragrant compounds in personal care emulsions(U.S. Pat. Nos. 5,525,588; 5,525,555; 5,490,982; and 5,372,806),encapsulation of a fragrant compound (U.S. Pat. Nos. 5,500,223;5,324,444; 5,185,155; 5,176,903; and 5,130,171), dissolving a fragrantcompound into a hydrophobic phase such as a silicone (U.S. Pat. Nos.5,449,512; 5,160,494 and 5,234,689), incorporation of a fragrantcompound into cross-linked polymers (U.S. Pat. Nos. 5,387,622 and5,387,411), incorporation of fragrant compounds into permeable laminates(U.S. Pat. Nos. 5,071,704 and 5,008,115), incorporation of fragrantcompounds into matrices that soften at body temperature (U.S. Pat. No.4,908,208), incorporation of fragrant compounds into rate controllingmembranes (U.S. Pat. No. 4,445,641) and derivatization of silanes withfragrant alcohols to form alkoxy silanes (U.S. Pat. Nos. 4,524,018 and4,500,725). All of these approaches suffer from one or more of thefollowing problems: 1) the material is not stable in a personal careformulation, 2) the material is not easy or convenient to prepare, or 3)the material does not release the fragrant compound in a slow andsustained fashion.

SUMMARY OF THE INVENTION

The present invention provides for A fragrance releasing siloxane havingthe formula:

    M.sub.f M.sup.F.sub.g D.sub.h D.sup.F.sub.i T.sub.j T.sup.F.sub.k Q.sub.l

where M has the formula R⁷ R⁸ R⁹ SiO_(1/2) ; M^(F) has the formula R⁷ R⁸R^(F) SiO_(1/2) ; D has the formula R¹⁰ R¹¹ SiO_(2/2) ; D^(F) has theformula R¹⁰ R^(F) SiO_(2/2) ; T has the formula R¹² SiO_(3/2) ; T^(F)has the formula R^(F) SiO_(3/2) ; and Q has the formula SiO_(4/2) whereR⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹² are each independently selected for each M,M^(F), D, D^(F), T and T^(F) from the group of one to forty carbon atommonovalent alkyl or alkoxy radicals and one to forty carbon atommonovalent aryl or aryloxy radicals where the subscripts f or g arepositive, and one or more of the subscripts h, i, j, k or l arepositive, subject to the limitation that one of the subscripts g, i, ork is one or greater than one; where R^(F) has the formula (R¹ O)_(a) (R²O)_(b) (R³ O)_(c) (R⁴)_(d) (R⁵)_(e) SiR^(U) with R^(U) a two to fortyatom divalent hydrocarbon radical where R¹ O, R² Oand R³ O are eachindependently fragrant alkoxide moieties, derived from the alcohols R¹OH, R² OH and R³ OH wherein R¹ OH, R² OH and R³ OH are independentlyfragrant alcohols with R⁴ and R⁵ selected from the group consisting ofmonovalent hydrocarbon radicals having from one to forty carbon atomsand monovalent alkoxy radicals having from one to forty carbon atoms,where the subscript a has a value ranging from 1 to 3 and the subscriptsb, c, d, and e have values ranging from 0 to 2 subject to the limitationthat a+b+c+d+e=3. The present invention also provides for compositionsthat comprise a fragrance releasing siloxane. Of particular use arecosmetic compositions that comprise a fragrance releasing siloxane.

DETAILED DESCRIPTION OF THE INVENTION

The compounds of the present invention introduce fragrant moieties viahydrosilylation of an olefinic silane molecule. These siloxane moleculesare useful in a variety of personal care compositions. The presentinvention is directed to new compositions of matter that are siloxanesthat release a fragrant alcohol upon hydrolysis.

The olefinic silanes utilized by the present invention are described bythe formula:

    (R.sup.1 O).sub.a (R.sup.2 O).sub.b (R.sup.3 O).sub.c (R.sup.4).sub.d (R.sup.5).sub.e SiR.sup.6

where R¹ O, R² O and R³ O fragrant alkoxide moieties, are selected (orderived from) from the group of alcohols consisting of R¹ OH, R² OH andR³ OH wherein R¹ OH, R² OH and R³ OH are fragrant alcohols with R⁴ andR⁵ selected from the group consisting of monovalent hydrocarbon radicalshaving from one to forty carbon atoms and monovalent alkoxy radicalshaving from one to forty carbon atoms, R⁶ a two to forty atom monovalentunsaturated hydrocarbon radical containing a terminal olefinic oracetylenic moiety where the subscript a has a value ranging from 1 to 3and the subscripts b, c, d, and e have values ranging from 0 to 2subject to the limitation that a+b+c+d+e =3. As used herein, the phrasemonovalent hydrocarbon radical includes both aliphatic and aromaticmonovalent hydrocarbon radicals that may also include hetero-atoms suchas oxygen, nitrogen, sulfur and the halogens, fluorine, chlorine,bromine and iodine.

The following synthetic examples are intended to illustrate the generalsynthetic reactions schemes that a person having ordinary skill in theart of silicones chemistry would typically employ in order to preparethe olefinic silanes used by the present invention. These reactionschemes are thus illustrative only and do not represent the onlysynthetic pathways that may be utilized.

When the starting material is a fragrant alcohol such as phenethanol,olefinic halosilanes or olefinic silicon alkoxides may be employed asstarting materials to produce the fragrance-releasing siloxanes of thepresent invention via fragrance bearing olefinic silanes.

Reaction scheme I: ##STR1## Reaction scheme II: ##STR2## Reaction schemeIII: ##STR3## Where the R groups for reaction III may be Et (C₂ H₅ --)or --CH₂ CH₂ C₆ H₅. Similarly3-methyl-5-(2,2,3,-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol willreact with chloromethylvinylsilane in a similar fashion, reaction schemeIV: ##STR4## as will allyldimethylchlorosilane react with citronellol ina similar, reaction scheme V: ##STR5##

The fragrant alcohols that are precursors of the silanes of the presentinvention are selected from the group consisting of3-methyl-5-(2,2,3,-trimethyl-3 -cyclopenten-1-yl)4-penten-2-ol,2-methylbutanol, 3-pentanol, n-pentanol, 2-pentanol, n-hexanol,2-methylpentanol, 1-decanol, sandela, nonadyl, dimetol, thymol,1-heptanol, menthol, eugenol, vanillan, o-vanillan,4-p-hydroxyphenyl)-2-butanone, syringealdehyde, prenol, cis-3-hexanol,trans-3-hexanol, cis-4-heptenol, trans-2-octenol,trans-2-cis-6-nonadienol, geraniol, nerol, citronellol, crotyl alcohol,oleyl alcohol, linalool, α-terpineol, β-phenethyl alcohol, cinnamicalcohol, benzyl alcohol, α-methylbenzyl alcohol, nonyl alcohol,1-octanol, 3-octanol, phenethyl salicylate, hydrocinnamyl alcohol,cis-6-nonen-1-ol, trans-2-nonen-1-ol, methyl salicylate, cis-3-octen-ol,anisyl alcohol, carvacrol, dihydrocarveol, benzyl salicylate,tetrahydrogeraniol, ethyl salicylate, ethyl vanillin, isoeugenol,isopulegol, lauryl alcohol, tetrahydrolinalool and 2-phenoxyethanol.

The fragrance releasing siloxanes of the present invention are preparedfrom an organohydrogen siloxane via conventional hydrosilylation usingthe fragrance bearing olefinic silane as the alkenyl source. Thus anorganohydrogensiloxane having the formula:

    M.sub.f M.sup.H.sub.g D.sub.h D.sup.H.sub.i T.sub.j T.sup.H.sub.k Q.sub.l

where M has the formula R⁷ R⁸ R⁹ SiO_(1/2) ; M^(H) has the formula R⁷ R⁸HSiO_(1/2) ; D has the formula R¹⁰ R¹¹ SiO_(2/2) ; D^(H) has the formulaR¹⁰ HSiO_(2/2) ; T has the formula R¹² SiO_(3/2) ; T^(H) has the formulaHSiO_(3/2) ; and Q has the formula SiO_(4/2) where R⁷, R⁸, R⁹, R¹⁰, R¹¹and R¹² are each independently selected for each M, M^(H), D, D^(H), andT from the group of one to forty carbon atom monovalent alkyl or alkoxyradicals and one to forty carbon atom monovalent aryl or aryloxyradicals where the subscripts f or g are positive, and one or more ofthe subscripts h, i, j, k or l are positive, subject to the limitationthat one of the subscripts g, i, or k is one or greater than one.

The organohydrogensiloxane is reacted under hydrosilylation conditionsto produce a fragrance releasing siloxane having the formula:

    M.sub.f M.sup.F.sub.g D.sub.h D.sup.F.sub.i T.sub.j T.sup.F.sub.k Q.sub.l

where the components and subscripts satisfy the previous definitions andrequirements and M^(F) has the formula R⁷ R⁸ R^(F) SiO_(1/2) ; D^(F) hasthe formula R¹⁰ R^(F) SiO_(2/2) ; and T^(F) has the formula R^(F)SiO_(3/2) ; where R^(F) has the formula (R¹ O)_(a) (R² O)_(b) (R³ O)_(c)(R⁴)_(d) (R⁵)_(e) SiR^(U) with R^(U) a two to forty atom divalenthydrocarbon radical where the subscripts and components are aspreviously defined. This non-volatile silicone undergoes a slowhydrolysis under most conditions of use whereby the silicone releases afragrant alcohol upon hydrolysis. This imparts a desirable odor to manydifferent useful compositions such as cosmetics and household products.

The hydrosilylation reaction is conventionally carried out in thepresence of a hydrosilylation catalyst selected from the group ofruthenium, osmium, rhodium, iridium, palladium and platinumhydrosilylation catalysts. Exemplary of such catalysts are thosedescribed in U.S. Pat. Nos. 2,823,218; 3,159,601; 3,159,662; and3,775,452.

The compositions of the present invention further provide that thefragrance releasing silicone have one or more substituents R¹, R², or R³where each substituent is independently selected whereby one fragrantalcohol resulting from hydrolysis of said silicone is selected from thegroup consisting of 2-methylbutanol, 3-pentanol, n-pentanol, 2-pentanol,n-hexanol, 2-methylpentanol, 1-decanol, sandela, nonadyl, dimetol,thymol, 1-heptanol, menthol, eugenol, vanillan,o-vanillan,4-(p-hydroxyphenyl)-2-butanone, syringealdehyde, prenol,cis-3- hexanol, trans-3-hexanol, cis-4-heptenol, trans-2-octenol,trans-2-cis-6-nonadienol, geraniol, nerol, ebanol, citronellol, crotylalcohol, oleyl alcohol, linalool, a-terpineol, b-phenethyl alcohol,cinnamic alcohol, benzyl alcohol, a-methylbenzyl alcohol, nonyl alcohol,1-octanol, 3-octanol, phenethyl salicylate, hydrocinnamyl alcohol,cis-6-nonen-1-ol, trans-2-nonen-1-ol, methyl salicylate, cis-3-octen-ol,anisyl alcohol, carvacrol, dihydrocarveol, benzyl salicylate,tetrahydrogeraniol, ethyl salicylate, ethyl vanilin isoeugenol,isopulegol, lauryl alcohol, tetrahydrolinalool and 2-phenoxyethanol.

The fragrance releasing compounds of the present invention areparticularly suited to incorporation into personal care products toimpart a desirable long lasting fragrance to the products. Suitable usesinclude but are not limited to deodorants, antiperspirants, skin creams,facial creams, hair care products such as shampoos, mousses, stylinggels, protective creams, shaving creams, after shave, cologne, perfume,color cosmetics such as lipsticks, foundations, blushes, makeup, andmascara; and other cosmetic formulations where other silicon containingcomponents have been added and where it is desirable to impart afragrance. Incorporation of small amounts of the compositions of thepresent invention into fragrance products such as shaving lotions,colognes, toilet water, and perfumes can impart a desirable long lastingfragrance to these products. Further, the silanes of the presentinvention may incorporated into other products where it is desirable tomask unpleasant odors with a pleasant fragrance for example householdcleaning products such as waxes and polishes, automobile cleaningproducts such as waxes and polishes, detergents, textile coatings,paints, varnishes and the like subject to the limitation that the silaneof the present invention be compatible or capable of being renderedcompatible with the product in which it is incorporated.

Experimental

Vinylsilanes 1-2 were prepared by phenethyl alcohol displacement on thecorresponding chlorosilanes. Vinylsilane 3 was a mixture of productsconsisting of 45% diethoxyphenethyloxy units, 39% ethoxydiphenethyloxyunits and 8% triphenethyloxy units that were made by equilibration of a1:1 mixture of triethoxyvinyl silane and phenethyl alcohol. Thesevinylsilanes were then attached to various hydrogen containing siloxanesto form the compositions of the present invention. In turn, 1-3 wereallowed to react with M^(H) D₂₅ M^(H), MD₂₀ D^(H) ₃ M and1,1,1,3,5,5,5-heptamethyltrisiloxane to give polymers 4-9 and siloxanes10-12 shown below. ##STR6## Hydrolysis Experiments:

Siloxane 10 was treated with a dilute base solution of NaOH and waterand the release of phenethyl alcohol, relative to an internal standard,was monitored by gas chromatography (GC). Table 1 shows that it tookabout 20 h for 50% of the fragrance to be released. In a similar manner,siloxane 11 and polymers 4 and 5 were treated with aqueous base toeffect the catalytic release of the fragrant alcohol. FIG. 1 shows thatthere was a much more rapid release of the alcohols from materials thatpossessed two alkoxy groups on a silicon. Compare 10 vs 11 and 4 vs 5.

Polymers 7-9 were also hydrolyzed with dilute base in a similar manner.Table 2 shows the polymer 8, with two phenethyloxy groups hydrolyzedfastest under these conditions and polymers 7 and 9 exhibited slowerrates of hydrolysis and had only about 50% of the alcohol released.

                  TABLE 1                                                         ______________________________________                                        Hydrolysis of Siloxanes 10-11 and Polymers 4-5                                  Siloxane 10 Siloxane 11 Polymer 4 Polymer 5                                 Time, %       Time,   %     Time,                                                                              %      Time,                                                                              %                                  hrs. Release hrs. Release hrs. Release hrs. Release                         ______________________________________                                        0.0   0.0     1.5     22.4  3.3  12.0   0.7  0.0                                2.38 4.6 3.1 42.5 21.0 37.1 3.3 56.4                                          4.5 6.6 18.2 77.6 46.0 47.8 19.9 92.0                                         21.2 52.5 42.3 88.7 141.8 51.0 27.0 92.9                                      46.0 55.1 72.0 88.1   44.0 89.5                                               165 53.6 140.9 99.6   97.3 94.0                                             ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                        Hydrolysis of Polymers 7-9.                                                     Polymer 7     Polymer 8      Polymer 9                                      Time, hrs.                                                                           % Release                                                                              Time, hrs.                                                                              % Release                                                                            Time, hrs.                                                                           % Release                             ______________________________________                                        0.5    8.5      0.1       7.8    0.1    10.8                                    4.4 16.3 3.8 41.5 3.6 24.8                                                    21.0 28.3 21.0 78.0 21.1 29.5                                                 45.5 40.3 45.4 96.7 45.5 33.0                                                 45.8 43.4 75.6 100.0 75.5 38.2                                                93.3 45.2 92.8 100.0 92.6 40.8                                              ______________________________________                                    

Preparation ofDimethylvinylphenethyloxysilane,1-Dimethylvinylchlorosilane (150 mL,1.099 moles) was added to a stirred solution of phenethyl alcohol (124.5mL, 1.042 moles), triethylamine (TEA, 155 mL, 1.112 moles) and toluene(300 mL) over 1.5 h. After addition, the reaction was heated to 65° C.for 0.5 h then cooled to room temperature, filtered, the filter cakewashed with toluene (200 mL), the filtrate concentrated in vacuo andthen vacuum distilled (81-85° C./4 mm Hg) to give product (180.5 g,84%).

Bis(phenethyloxy)methylvinylsilane, 2-Dichloromethylvinylsilane (80 g,0.567 moles) was added to a stirred solution of phenethyl alcohol (140g, 114 moles), triethylamine (TEA, 121 g, 1.2 moles) and Isopar C (700mL) over one hour during which time the reaction mixture was heated to70° C. After an additional one hour, the reaction was cooled to roomtemperature, filtered, concentrated in vacuo and then stripped underhigh vacuum distilled (110° C. /4 mm Hg) to give product (166 g, 94%).

Phenethyloxydiethoxymethylvinylsilane, 3-Triethoxyvinylsilane (200 g,1.05 moles), phenethyl alcohol (128 g, 1.05 moles) and Filtrol-20(5 g)were added together and heated to 90° C. Ethanol (EtOH) was distilledoff as it formed and the reaction was stopped when most of the phenethylalcohol had been consumed. The reaction mixture was then stripped at 90°C./ 4 mm Hg to give a mixture of products which had the followingdistribution: 45% 3, in which both OR=OEt, 39% 3, in which one OR=OEtand one OR=phenethyloxy, and 8% 3 in which both OR=phenethyloxy.

Terminally Substituted Polymer 4 - Polymer M^(H) D₂₅ M^(H) (80 g, 0.044moles) was added slowly to a solution of vinylsilane 1 (18.2 g, 0.088moles) and platinum catalyst (10 mg). When addition was complete thetemperature was raised to 80° C. for 2 h then cooled, filtered throughCelite to give 90.6 g of a clear colorless liquid.

Terminally Substituted Polymer 5 - Polymer M^(H) D₂₅ M^(H) (60 g, 0.033moles) was added slowly to a solution of vinylsilane 2 (20.6 g, 0.066moles) and platinum catalyst (10 mg) at 60° C. When addition wascomplete the temperature was kept at 60° C. for 4 h the raised to 80° C.for 1 h then cooled and filtered through Celite to give 68.0 g product.

Terminally Substituted Polymer 6 - A solution of vinylsilane 3 (20.6 g,0.066 moles) and platinum catalyst (8 mg) was slowly added to hydridepolymer M^(H) D₂₅ M^(H) at 80° C. When addition was complete thetemperature was kept at 80° C. for 8 h then cooled, stripped at highvacuum (130° C./4 mm Hg) and filtered through Celite to give 76.9 gproduct.

Graft Copolymer 7 - Polymer MD₂₀ D^(H) ₃ M (80 g, 0.044 moles) was addedslowly to a solution of vinylsilane 1 (27.2 g, 0.132 moles) and platinumcatalyst (10 mg) at 60° C. When addition was complete the reaction wasallowed to react for an additional 2 h then cooled and filtered throughCelite to give a clear colorless liquid (98.8 g).

Graft Copolymer 8 - Polymer MD_(2O) D^(H) ₃ M (100 g, 0.055 moles) wasadded slowly to a solution of vinylsilane 2 (51.5 g, 0.165 moles) andplatinum catalyst (10 mg) at 60° C. During addition the temperature wasraised to 90° C. When addition was complete the reaction was allowed toreact for an additional 4 h then more catalyst was added (10 mg), heated5 more hours, another aliquot of catalyst added (10 mg) and additionalheating for 7 h. The mixture was then stripped under high vacuum (90°C./4 mm Hg) and filtered through Celite to give 133.3 g product.

Graft Copolymer 9 - to a solution of vinylsilane 3 (30.9 g, 0.099 moles)and platinum catalyst (10 mg) was added slowly to polymer MD₂₀ D^(H) ₃ M(60 g, 0.033 moles) at 90° C. and allowed to react for 8 h. Twoadditional aliquots of catalyst (10 mg each) were added over 16additional hours of heating. The mixture was then stripped under highvacuum (100° C./4 mm Hg) and filtered through Celite to give 75.0 gproduct.

Siloxane 10 - Heptamethyltrisiloxane (40 g, 0.18 moles) was added slowlyto a solution of vinylsilane 1 (37 g, 0.18 moles) and platinum catalyst(6 mg) at 60° C. When addition was complete the reaction was allowed toreact for an additional 1 h then distilled (˜150° C. /4 mm Hg) to give53.4 g product.

Siloxane 11 - Heptamethyltrisiloxane (20 g, 0.09 moles) was added slowlyto a solution of vinylsilane 2 (28.1 g, 0.09 moles) and platinumcatalyst (6 mg) at 60° C. When addition was complete the reaction wasallowed to react for an additional 0.5 h at 80° C. then cooled andfiltered to give 43.0 g product.

Siloxane 12 - Heptamethyltrisiloxane (40 g, 0.18 moles) was added slowlyto a solution of vinylsilane 3 (56.1 g, 0.18 moles) and platinumcatalyst (10 mg) at 70° C. When addition was complete the reaction wasallowed to react for an additional 12 h at 90° C. with one additionalcatalyst (10 mg) addition. The mixture was then cooled stripped underfull vacuum (100° C. /4 mm Hg) and filtered to give 89.2 g product.

Hydrolysis of Siloxane 10 - Siloxane 10 (216 mg, 0.505 mmol) andbibenzyl (68.3 mg, 0.375 mmol) were dissolved in THF (2.0 g) and thentreated with 1 wt % NaOH in water (100 mL). Aliquots were removed attimed intervals for GC analysis.

Hydrolysis of Siloxane 11 - Siloxane 11 (117.5 mg, 0.220 mmol) andbibenzyl (33.1 mg, 0.182 mmol) were dissolved in THF (2.0 g) and thentreated with 1 wt % NaOH in water (100 mL). Aliquots were removed attimed intervals for GC analysis.

Hydrolysis of Polymer 4 - Polymer 4 (206.4 mg, 0.092 mmol) and bibenzyl(25.8 mg, 0.141 mmol) were dissolved in THF (2.0 g) and then treatedwith 1 wt % NaOH in water (40 mL). Aliquots were removed at timedintervals for GC analysis.

Hydrolysis of Polymer 5 - Polymer 5 (211.6 mg, 0.086 mmol) and bibenzyl(50.6 mg, 0.278 mmol) were dissolved in THF (2.0 g) and then treatedwith 1 wt % NaOH in water (80 mL). Aliquots were removed at timedintervals for GC analysis.

Hydrolysis of Polymer 7 - Polymer 7 (1368.9 mg, 0.083 mmol) and bibenzyl(50.2 mg, 0.275 mmol) were dissolved in THF (2.0 g) and then treatedwith 1 wt % NaOH in water (55 mL). Aliquots were removed at timedintervals for GC analysis.

Hydrolysis of Polymer 8 - Polymer 8 (187.8 mg, 0.068 mmol) and bibenzyl(59.3 mg, 0.325 mmol) were dissolved in THF (2.0 g) and then treatedwith 1 wt % NaOH in water (90 mL). Aliquots were removed at timedintervals for GC analysis.

Hydrolysis of Polymer 9 - Polymer 9 (117.1 mg, 0.042 mmol) and bibenzyl(59.1 mg, 0.324 mmol) were dissolved in THF (2.0 g) and then treatedwith 1 wt % NaOH in water (45 mL). Aliquots were removed at timedintervals for GC analysis.

Having described the invention that which is claimed is:
 1. A fragrancereleasing siloxane having the formula:

    M.sub.f M.sup.F.sub.g D.sub.h D.sup.F.sub.i T.sub.j T.sup.F.sub.k Q.sub.l

where M has the formula R⁷ R⁸ R⁹ SiO_(1/2) ; M^(F) has the formula R⁷ R⁸R^(F) SiO_(1/2) ; D has the formula R¹⁰ R¹¹ SiO_(2/2) ; D^(F) has theformula R¹⁰ R^(F) SiO_(2/2) ; T has the formula R¹² SiO_(3/2) ; T^(F)has the formula R^(F) SiO_(3/2) ; and Q has the formula SiO_(4/2) whereR⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹² are each independently selected for each M,M^(F), D, D^(F), T and T^(F) from the group of one to forty carbon atommonovalent alkyl or alkoxy radicals and six to forty carbon atommonovalent aryl or aryloxy radicals where the subscripts f or g arepositive, and one or more of the subscripts h, i, j, k or l arepositive, subject to the limitation that one of the subscripts g, i, ork is one or greater than one; where R^(F) has the formula (R¹ O)_(a) (R²O)_(b) (R³ O)_(c) (R⁴)_(d) (R⁵)_(e) SiR^(U) with R^(U) a two to fortyatom divalent hydrocarbon radical where R¹ O, R² O and R³ O are eachindependently fragrant alkoxide moieties, derived from the alcohols R¹OH, R² OH and R³ OH wherein R¹ OH, R² OH and R³ OH are independentlyfragrant alcohols with R⁴ and R⁵ selected from the group consisting ofmonovalent hydrocarbon radicals having from one to forty carbon atomsand monovalent alkoxy radicals having from one to forty carbon atoms,where the subscript a has a value ranging from 1 to 3 and the subscriptsb, c, d, and e have values ranging from 0 to 2 subject to the limitationthat a+b+c+d+e=3.
 2. The fragrance releasing siloxane of claim 1 whereinthe subscript a has a value of
 2. 3. The fragrance releasing siloxane ofclaim 1 wherein the subscript a has a value of
 3. 4. The fragrancereleasing siloxane of claim 1 where the subscript 1 is
 0. 5. Thefragrance releasing siloxane of claim 4 where the subscript k is
 0. 6.The fragrance releasing siloxane of claim 5 where the subscript j is 0.7. The fragrance releasing siloxane of claim 6 where the subscript i is0.
 8. The fragrance releasing siloxane of claim 7 where the subscript jis
 0. 9. The fragrance releasing siloxane of claim 7 where the subscriptg is
 0. 10. The fragrance releasing siloxane of claim 7 where R¹, R² andR³ are derived from the group of fragrant alcohols consisting of2-methylbutanol, 3-pentanol, n-pentanol, 2-pentanol, n-hexanol,2-methylpentanol, 1-decanol, sandela, nonadyl, dimetol, thymol,1-heptanol, menthol, eugenol, vanillan, o-vanillan,4-(p-hydroxyphenyl)-2-butanone, syringealdehyde, prenol, cis-3-hexanol,trans-3-hexanol, cis-4-heptenol, trans-2-octenol,trans-2-cis-6-nonadienol, geraniol, nerol, ebanol, citronellol, crotylalcohol, oleyl alcohol, linalool, a-terpineol, b-phenethyl alcohol,cinnamic alcohol, benzyl alcohol, a -methylbenzyl alcohol, nonylalcohol, 1-octanol, 3-octanol, phenethyl salicylate, hydrocinnamylalcohol, cis-6-nonen-1-ol, trans-2-nonen-1-ol, methyl salicylate,cis-3-octen-ol, anisyl alcohol, carvacrol, dihydrocarveol, benzylsalicylate, tetrahydrogeraniol, ethyl salicylate, ethyl vanillin,isoeugenol, isopulegol, lauryl alcohol, tetrahydrolinalool and2-phenoxyethanol.
 11. A fragrance releasing siloxane comprising asubstituent having the formula:

    (R.sup.1 O).sub.a (R.sup.2 O).sub.b (R.sup.3 O).sub.c (R.sup.4).sub.d (R.sup.5).sub.e SiR.sup.U

with R^(U) a two to forty atom divalent hydrocarbon radical where R¹ O,R² O and R³ O are each independently fragrant alkoxide moieties, derivedfrom the alcohols R¹ OH, R² OH and R³ OH wherein R¹ OH, R² OH and R³ OHare independently fragrant alcohols selected from the group consistingof 2-methylbutanol, 3-pentanol, n-pentanol, 2-pentanol, n-hexanol,2-methylpentanol, 1-decanol, sandela, nonadyl, dimetol, thymol,1-heptanol, menthol, eugenol, vanillan, o-vanillan,4-(p-hydroxyphenyl)-2-butanone, syringealdehyde, prenol, cis-3-hexanol,trans-3-hexanol, cis-4-heptenol, trans-2-octenol,trans-2-cis-6-nonadienol, geraniol, nerol, ebanol, citronellol, crotylalcohol, oleyl alcohol, linalool, a-terpineol, b-phenethyl alcohol,cinnamic alcohol, benzyl alcohol, a -methylbenzyl alcohol, nonylalcohol, 1-octanol, 3-octanol, phenethyl salicylate, hydrocinnamylalcohol, cis-6-nonen-1-ol, trans-2-nonen-1-ol, methyl salicylate,cis-3-octen-ol, anisyl alcohol, carvacrol, dihydrocarveol, benzylsalicylate, tetrahydrogerariol, ethyl salicylate, ethyl vanillin,isoeugenol, isopulegol, lauryl alcohol, tetrahydrolinalool and2-phenoxyethanol with R⁴ and R⁵ selected from the group consisting ofmonovalent hydrocarbon radicals having from one to forty carbon atomsand monovalent alkoxy radicals having from one to forty carbon atoms,where the subscript a has a value ranging from 1 to 3 and the subscriptsb, c, d, and e have values ranging from 0 to 2 subject to the limitationthat a+b+c+d+e=3.